Lubricating composition

ABSTRACT

A lubricating oil composition having good shear stability is obtained by blending together a mineral lubricating oil and a viscosity index improving amount of a polymer of a normal alpha olefin having from four to 16 carbon atoms per molecule. The polymer is obtained by polymerizing the alpha olefin or alpha olefin mixture in the liquid phase in the presence of aluminum chloride and a nonpolymerizing hydrocarbon diluent at a temperature between about -40* and +70* F. for a time sufficient to produce a polymer having a viscosity of about 40 to about 3000 centistokes at 210* F. The alpha olefin is introduced into the polymerization system at a rate of about 0.6 to about 60 moles of olefin per mole of aluminum chloride per hour. The addition of the olefin is continued until 2 to 200 moles of olefin per mole of aluminum chloride has been added.

United States Patent Giannetti et al.

Jan. 25, 1972 LUBRICATING COMPOSITION [72] Inventors: Joseph P.Giannetti, Allison Park; Robert A. Plundo, Greensburg, both of Pa.

[73] Assignee: Gulf Research 8! Development Company,

Pittsburgh, Pa.

[22] Filed: July 28, 1969 [211 App]. No.: 845,502

[52] US. Cl ..252/59 [51] Int. Cl. ..C10m 1/16 [58] Field of Search..252/59; 260/93.74

[56] References Cited UNITED STATES PATENTS 2,525,788 10/1950 Fontana etal. ..252/59 2,697,694 12/1954 Shalit et al. .252/59 2,779,753 l/1957Garabrant et al ..252/59 X Primary Examiner-Daniel E. Wyman AssistantExaminer-W. J. Shine Attorney-Meyer Neishloss, Deane E. Keith andWilliam H. Deitch [5 7] ABSTRACT A lubricating oil composition havinggood shear stability is obtained by blending together a minerallubricating oil and a and +70 F. for a time sufficient to produce apolymer having a viscosity of about 40 to about 3000 centistokes at 210F.

The alpha olefin is introduced into the polymerization system at a rateof about 0.6 to about 60 moles of olefin per mole of aluminum chlorideper hour. The addition of the olefin is continued until 2 to 200 molesof olefin per mole of aluminum chloride has been added.

10 Claims, No Drawings LUBRICATING COMPOSITION This invention relates toa lubricating oil composition and more particularly to a minerallubricating oil composition having improved viscosity indexcharacteristics.

The viscosity-temperature relationship of a lubricating oil is one ofthe more important characteristics of an oil in that it is thisrelationship which is indicative of the relative change in viscosity ofan oil at high and low temperatures. As might be expected, the viscosityof most mineral lubricating oils changes rapidly with a change in theirtemperature. In general, mineral oils tend to become thinner as theirtemperature increases and thicker as their temperature decreases. Thechange in viscosity with temperature is greater with some oils than withothers. While some change is tolerable, excessive change is undesirable.In motor oils of the type known as crankcase oils, it is desirable forthe oil to have a viscosity which is sufficiently high at an elevatedtemperature to provide adequate lubrication and to prevent excessive oilconsumption. On the other hand, the motor oil should have a viscositywhich is sufficiently low at ambient temperature to provide ease ofengine starting. Increasing the high-temperature viscosity of an oilwhile decreasing its low-temperature viscosity can be accomplished onlyby improving the viscositytemperature relationship or, stateddifferently, by raising the viscosity index of the oil. g

In the past, the viscosity index of a mineral lubricating oil has beenimproved by subjecting the base oil from which the lubricating oilcomposition is made to more drastic refining methods and/or by adding aviscosity index improver to the lubricating oil. For example, theviscosity index of some oils has been improved by subjecting the baseoil to solvent extraction and treatment with aluminum chloride. Aluminumchloride refined or solvent extracted paraffinic oils, such as thePennsylvania oils, have provided excellent base oils for manylubricating compositions having improved viscosity indices. Likewise,drastically refined Mid-Continent and Gulf Coastal oils have been widelyused as base oils in forming lubricants having high-viscosity indices.

In addition to these refining methods, lubricating oils of improvedviscosity indices have been obtained by hydrogenating various chargestocks derived from Pennsylvania, Mid-Continent, West Coast, Middle-Eastcrudes, etc. It is known, for example, that improvedviscosity-temperature relationships can be obtained when somelubricating oil stocks are either hydrofinished or hydrotreated.I-Iydrofinishing and hydrotreating some lubricating oil stocks, forexample, has resulted in excellent base stocks for multigradelubricants, i.e., lubricants suitable for use under a wide range oftemperatures. Regardless of the treatment to which the various chargestocks are subjected, the viscosity index of the lubricating oil can beimproved only up to a certain maximum by refining techniques aloneinasmuch as further treatment has only an additional negligible effecton viscosity index characteristics. Further improvement can be effectedby adding various types of viscosity index improving additives to thelubricating oil. In improving the viscosity index of lubricating oils byadditives, recourse has been made to the introduction of various highmolecular weight polymers such as polyisobutylene, polymerized esters ofthe acrylic acid series and the like. In most instances, the highestincrease in viscosity index is obtained with polymers of the greatestmolecular weight. While high molecular weight polymers have beengenerally satisfactory in improving the viscosity-temperaturerelationship of the oil, these polymers have not been entirelysatisfactory inasmuch as their viscosity index improving characteristicin many instances is lost or substantially reduced when the oil in whichthey are incorporated is subjected to vigorous agitation and high shearrates and stresses.

We have found that a lubricating composition having a high-viscosityindex and improved shear stability is obtained by incorporating in amineral lubricating oil a minor amount, sufficient to improve theviscosity index of said oil, of a polymer of a normal alpha olefinhaving about four to about 16 carbon atoms per molecule or a polymer ofa mixture of normal alpha olefins where the average carbon number ofthemixture is about four to about l6, said polymer being obtained by theprocess which comprises polymerizing said olefin in the liquid phase inthe presence of aluminum chloride and a nonpolymerizing hydrocarbondiluent, said olefin being introduced into the aluminumchloride-nonpolymerizing hydrocarbon reaction mass at a rate of about0.6 to about 60 moles of said olefin per mole of aluminum chloride perhour and in an amount of about 2 to about 200 moles of olefin per moleof aluminum chloride, at a temperature of about 40 to about +70 F. for atime sufficient to produce a polymer having a viscosity of about 40 toabout 3,000 centistokes at 210 F. We have found that a lubricatingcomposition comprising a major=amount of a mineral lubricating oil and aminor amount of a polymer obtained as described above in addition tobeing shear stable is also thermally stable.

In accordance with the invention, normal alpha olefins having about fourto about 16 carbon atoms per molecule or a blend of normal alpha olefinswhere the average carbon number of the blend is between about four andabout 16 are polymerized in high yield by a process which comprisescontacting theolefin or blend of olefins in the liquid phase withaluminum chloride catalyst in a nonpolymerizing hydrocarbon solvent at atemperature of about 40 to about +70 F. under selected and correlatedreaction conditions to give a polymer having a viscosity of about 40 toabout 3,000 centistokes at 210 F. While we recognize that alpha olefinshave been polymerized previously in the presence of aluminum chloride oraluminum bromide, a catalyst promoting agent and a nonpolymerizinghydrocarbon diluent, we have discovered that, by carrying out thepolymerization reaction under selected and correlated reactionconditions, shear stable polymers having viscosities of about 40 toabout 3,000 centistokes at 210 F. are obtained and that these polymerswhen added to a mineral lubricating oil in amounts sufficient to improvethe viscosity index of the oil produce a lubricating composition havinggood shear and thermal stability. The polymers obtained in accordancewith the present invention not only improve the viscosity index of mostmineral lubricating oils but also impart exceptional multiviscositycharacteristics to certain hydrotreated mineral lubricating base oils,said multiviscosity characteristics heretofore having been obtained byutilizing compounds or compositions comprising constituents other thanhydrocarbons, e.g., polymerized esters of the acrylic acid series.

The polymers obtained in accordance with the present invention can beincorporated in the mineral lubricating oil in any convenient manner.Thus, the polymers as such, can be added directly to the lubricating oilor they can be added in the form of concentrated solutions in a solventsuch as a light lubricating oil in order to facilitate blending. Ifdesired, such concentrated solutions also can contain other compatibleaddition agents designed to improve one or more properties of the oil.In the case of blended lubricating oils, the herein-disclosed polymerscan be added to one of the component oils prior to blending. Somestirring, possibly with mild heating may be desirable to facilitate morerapid formation of a homogeneous mixture, but this is not absolutelyessential.

Exemplary of the alpha olefins which are used in preparing the polymersaccording to the invention are butene-l, pentene-l, hexene-l, heptene-l,octene-l, nonene-l, decene-l, undecene-l dodecene-l, tridecene-l,tetradecene-l pentadecene-l, hexadecene-l and mixtures thereof.

In preparing lubricating compositions of the present invention, thepolymers are employed in concentrations in the range of about 2 to about30 percent preferably about 5 to about 25 percent by volume based on thevolume of the final lubricating composition, but other proportions canbe used provided that the polymer is soluble in the oil to the extent towhich it is used. The optimum amount of polymer employed may varydepending upon the characteristics of the particular polymer employedand upon the characteristics of the base oil to which the polymer is tobe added. Ordinarily, a polymer having a high viscosity will be used inamounts less than a polymer having a low viscosity. ln any event, thepolymer is added to the lubricating oil in an amount sufficient toimprove the viscosity index of the oil. An especially shear stablelubricating composition having a high-viscosity index has been obtainedby admixing about 8 to 10 percent by volume of a decene-lpolymer havinga viscosity of about 380.7 cs. (1770 SUS) at 210 F. with about 90 to 92percent by volume of a hydrotreated mineral lubricating oil.

In preparing the polymers utilized in the composition of the presentinvention, the alpha olefin or alpha olefin mixture is introduced into areaction vessel containing aluminum chloride catalyst and anonpolymerizing hydrocarbon diluent. Prior to introducing the alphaolefin into the reaction vessel, the mixture of aluminum chloride andnonpolymerizing hydrocarbon diluent is preferably contacted withhydrogen chloride for a short time, usually not more than about 1 to 2hours, preferably about to 30 minutes. Such contacting can be conductedmerely by bubbling gaseous hydrogen chloride through the mixture ofaluminum chloride and nonpolymerizing hydrocarbon diluent. The diluentis preferably a paraffin hydrocarbon such as butane. However, othernonpolymerizing hydrocarbon diluents can be used. The amount of thediluent may be the same that is normally used in other olefinpolymerization reactions. For example, we may use the nonpolymerizinghydrocarbon diluent in amounts of about 1 to about 15 moles per mole ofolefin. Larger or smaller amounts may be employed as desired.

The polymerization reaction is carried out generally with agitation at atemperature of about 40 to about +70 F., preferably at a temperature ofabout to about +40 F. The pressure should be just sufficient to keep thealpha olefin in the liquid phase. Higher pressures have no advantage.While the rate at which the alpha olefin is introduced into the reactionvessel can vary over wide limits, we prefer to add the olefin to thereaction mixture at a rate of about 0.6 to about 60 moles of olefin permole of aluminum chloride per hour, preferably about 2 to about 20 molesof alpha olefin per mole of aluminum chloride per hour. The amount ofalpha olefin added comprises about 2 to about 200 moles of alpha olefinper mole of aluminum chloride, preferably about l0 to about I50 moles ofalpha olefin per mole of aluminum chloride. The reaction time issufficient to produce a polymer having a viscosity of about 40 to about3,000 eentistokes at 2l0 F. ln most instances, polymerization o thisextent is complete in about I to about 24 hours, and usually in about 3to about l2 hours. In a preferred embodiment of the invention, a shearstable lubricating composition is obtained by incorporating in a minerallubricating oil a minor amount, sufficient to improve the viscosityindex of the oil, of a polymer of decene-l, said polymer being obtainedby the process which comprises polymerizing said decene-lin the liquidphase in the presence of aluminum chloride and butane as a diluent, saiddecenelbeing introduced into the aluminum chloride-butane reaction massat a rate of about 2 to about 12 moles of decenelper mole of aluminumchloride per hour and in an amount of about 10 to about I00 moles ofdecene-lper mole of aluminum chloride, at a temperature of about 25 toabout 35 F. for a time sufficient to produce a polymer having aviscosity of about 40 to about 3,000 centistokes at 210 F. Inasmuch asthe polymerization reaction is exothermic, means must be provided forremoving heat during the polymerization. In a preferred embodiment theheat of reaction is removed by a heat exchanger through which a coolantcirculates at about l0 to about 20 F. below the boiling point of thediluent. If desired, evaporative cooling can be effected by vaporizationof the diluent from the reaction mass. At the conclusion of thepolymerization reaction, the contents of the reaction vessel are emptiedinto a quantity of water, i.e., about 0.5 to about 20 times the volumeof the reaction mass to decompose the catalyst. The polymer is separatedfrom the water and then dried. The dried polymer is subjected to atopping distillation to 700' F. The polymer thus obtained has aviscosity within the range of40 to 3,000 centistokes at 210 F.

The lubricating oil to which the polymerized alpha olefin is addedaccording to the invention is advantageously a highly refined oilderived from a paraffinic, naphthenic or asphalt base oil. Thus, thelubricating oil can be one which has been obtained by conventionalaluminum chloride refining and/or by solvent extraction. Aluminumchloride refined or solvent extracted paraffinic base oil, such asPennsylvania oil, provides an excellent base oil for the composition ofthe invention. However, drastically refined Mid-Continent and GulfCoastal oil may also be used. Hydrofinished and hydrotreated mineraloils, because of their improved stability over untreated oils and alsotheir improved viscosity index characteristics are especially preferredlubricating oil bases for preparing multigrade lubricating compositionsof the invention. Hydrotreating is distinguished from hydrofinishing inthat the latter involves the use of milder hydrogenation conditions. Inthis regard, we prefer to employ an oil which has been hydrotreated.While hydrotreated oils are excellent base oils from which multigradelubricants can be prepared according to the invention, we can alsoobtain multigrade lubricating oils using a hydrofinished orconventionally refined base oil.

Especially preferred hydrotreated oils are obtained when a deasphaltedresiduum is treated with hydrogen at a temperature within theapproximate range of about 650 to about 850 F.; a pressure within therange of 1,500 to about 10,000 p.s.i.g.; a space velocity between about0.l and about 5 volumes of charge stock per volume of catalyst per hour;and a hydrogen recycle rate between about 2,000 and about 7,500 standardcubic feet per barrel of charge. A preferred set of operating conditionsfor hydrotreating include a temperature of 700 to 800 F., a pressure of2,000 to 5,000 p.s.i.g., a space velocity of 0.25 to 2 and a gascirculation rate of 2,500 to 5,000 standard cubic feet of hydrogen perbarrel of charge.

The viscosity index improving characteristics and shear stability oflubricating compositions containing the polymers of normal alpha olefinsaccording to the invention will hereinafter be illustrated using variouslubricating oil bases. It will be noted that many of the illustrativelubricating compositions satisfy the SAE viscosity requirements ofmultigrade lubricants.

The preparation of the polymers of C to C, normal alpha olefins utilizedin compositions of the invention will be illustrated by the followingspecific examples.

EXAMPLE I Into a 3-liter, three-necked flask equipped with a stirrer, acondenser and a gas inlet tube was placed 1,465 ml. (15.1 moles) ofbutane and l 1.0 grams (0.08 mole) of aluminum chloride. Hydrogenchloride gas as a promoter was bubbled through the stirred system forapproximately 15 minutes. Decene-l (1,284 ml. [6.78 molesl) was added tothe reaction vessel over an 8-hour period. The reaction ratios were asfollows:

Moles of deccnc-l per mole of AlCl 84.8 Moles of butane per mole ofdecenc-l 2.23 Moles of decene-l per mole of MCI, per hour l0.6

The temperature of the reactants was maintained at 30 F. After all thedecene-l had been added, the contents of the flask were poured into avessel containing 1 liter of heptane and 2 liters of water. The butanewas removed from the reaction mass by vaporization. After all the butanewas removed, the heptane-polymer mixture was washed three times with 1.5liters of water. The washed product was dried over anhydrous sodiumsulfate and then fractionated by distillation. The yield of polymerhaving an initial boiling point of 700 F. was percent based on thevolume of the decene-l charged. The polymer thus obtained had aviscosity of 380.7 cs. (1770 SUS) at 210 F. and a viscosity index of 115.

This decene-l polymer was blended with various hydrotreated base oils.lnspections of the physical properties of these blends are shown intable I.

TABLE I Percent by volume of Composition...

TABLE III Percent by volume of Composition I J K L M N Hyd rotreatcdbase oil: 5 Deeene-l pol mer 10 15 Acryloid I improver 3 4 5inspections. Viscosity at 210 F., cs.: y Before sonic shear Stu,Inspgctions; bility test 5-95 4-25 1]. 62 7. 81 8. 56 10.1!) 7. 02

Viscosity t Aiter sonic shear sta- 210 F.,cs 5.60 .10 6.22 380.7 10.7911.33 9.79 10 il y test 5-95 4.25 9.58 7. 23 7.70 10. 11 6.86 Viscosityi Viscosity index, D567:

D5 7 13 132 135 115 142 140 139 B fo some sh ar sta- Pour point o o 5 00 billty test 130 00 136 146 14!; 138 152 After sonic shear stabilitytest 120 90 130 142 143 138 146 Pereent loss in thickening l )1 When90.0 volume percent of a hydrotreated base oil 15 power 1 31 33 1designated as hydrotreated base oil 1 was blended with 10 volume percentof the decene-l polymer, the resulting lubricating composition(Composition E) met the viscosity specifications of a multigrade l0W/30lubricating oil, having a viscosity of 10.79 cs. at 2 10 F. and aviscosity index of 142.

When 90.0 volume percent of a hydrotreated base oil designated ashydrotreated base oil 2 was blended with 10 volume percent of thedecene-l polymer, the resulting lubricating composition (Composition F)met the viscosity specifications of a multigrade l0W/30 lubricating oilhaving a viscosity of 1 1.33 cs. at 2 10 F. and a viscosity index of M0.

When 91.75 volume percent of a hydrotreated base oil designated ashydrotreated base oil 3 was blended with 8.25 volume percent of thedecene-l polymer, the resulting lubricating composition (Composition G)met the viscosity specifications of a multigrade l0W/30 lubricating oilhaving a viscosity of 9.79 cs. at 2 1 0 F. and a viscosity index of 139.

The excellent sonic shear stability of the oils prepared in example l isillustrated using the blend prepared by adding 8.25 volume percent ofthe decene-l polymer to the hydrotreated base oil designated ashydrotreated base oil 3 (Composition G). In order to illustrate theshear stability of the polymers of the invention, the polymer-base oilblends are subjected to a proposed ASTM test for detennining the shearstability of polymer containing oils. This test is described in ASTMStandards on Petroleum Products. Volume 1, 1961, page l,l60. Accordingto this test, the material to be evaluated is subjected to irradiationin a sonic oscillator for a fixed period of time and the change inviscosity determined. The results ob- An additional hydrotreated baseoil as well as a hydrofinished light neutral distillate oil were blendedwith the decene-l of example 1. For comparison, these oils were alsoblended with a conventional Acryloid viscosity improving agent. Theresults obtained are presented in table lll.

TABLE III Percent by volume of- Composition H I J K L M N Hydrotreatcdbase oi14..... 100 90 97 06 Hydrofinished light neutral distillateojl,100 85 05 I V=hlend viscosity at 210 F. after shear test.

Vn=viscosity of base oil at 210 F. before shear test.

where The improved shear stability obtained with the decene-l polymer inaccordance with the present invention as compared with a conventionalAcryloid viscosity index improver is clearly shown by the illustrativedata in table ill. It will be noted that after sonic irradiation,compositions of the invention, i.e., Compositions .l and M, retainedtheir highviscosity indices with very little loss in thickening power.Contrariwise, the hydrotreated and hydrofinished base oils containingthe Acryloid" viscosity index improver did not retain theirhigh-viscosity index and lost from 29 to 33 percent of their thickeningpower. The data thus obtained in the sonic shear stability test indicatethat the alpha olefin polymers are surprisingly more stable thanconventional Acryloid" viscosity index improvers even when subjected tovigorous agitation and high shear rates and stresses.

The thermal stability of a lubricating composition of the invention isdemonstrated by the data in table IV. In order to illustrate the thermalstability of polymers utilized in compositions of the invention, theblends were subjected to a modified London Heat Test. According to thistest, the material to be evaluated is heated to l60 F. for 48 hours andthe change in color is determined by ASTM D1500.

These-tests were conducted with a hydrofinished light neutral distillateoil and the decene-l polymer of example 1.

.For comparison, an additional composition was prepared utilizing aconventional Acryloid viscosity index improving agent. In these tests,the lubricating composition was subjected to a temperature of 500 F. for24 hours under an atmosphere of nitrogen.

The improved thermal stability obtained with an olefin polymer inaccordance with the present invention as compared with a conventionalAcryloid viscosity index improver is clearly shown by the illustrativedata in table IV. it will be noted that the oil with the decene-lpolymer did not show any viscosity loss or increase in acidity(neutralization number) after exposure to 500 F. for 24 hours in anitrogen atmosphere. The oil which contained the Acryloid" viscosityindex improver lost l2 percent of its thickening power and showed anincrease in neutralization number after exposure to the same conditions.

TAB LE IV Percent by volume of Composition I M Tv Hydrofinished lightneutral distillate Oil 86 05 Decene-l olymer VI Improver P hysiealcharacteristics Viscosity at 210 F., cs.:

WHEEL TABLE IV Percent by volume of Composition I M Color, ASTM D1500:

Before heating to 500 F 1. 1. 0 1. After heating to 500 F 1. 1.5 1.Percent loss in thickening power I 0 1 I Loss in thickening powcr=Vr-V IV1-Vl where bicn(1 viscosity at 210 F. before thermal test.

V:blend viscosity at 210 F. after thermal test. vo yiscosity ofl ase oilat 210 F. before thermal test.

recto EXAMPLES 2 to l 1 inspections;

Viscosityat 210 F..es.... 4.25 10.2 10.2 10.2 10.2 10.2 10.2 Viscosityindex, D667. J0 133 135 138 13'.) 141 142 Pour point, F 0 +5 +5 0 +10+20 Sonic shear test (10 minutcs) 210' F. viscosity loss, cs less than1% of original viscosity Viscosity index loss Less then 1% of originalviscosity index otherpror rtieso f Q nposition iii are shown in Tables111 and 1\".

All the blended oils shown in table Vl are shear stable, i.e., less thani percent loss in viscosity or viscosity index. The blended oilsprepared from the polymers where the alpha olefin monomer contained sixand eight carbons while having improved viscosity index characteristicswere marginal oils with respect to the viscosity index. The blended oilsfrom the polymers where the alpha olefin monomer contained 12 to 16carbons had high pour points which, however, can be reduced by the useof a pour point depressant. The blended oils containing the decene-lpolymer, when both the viscosity index and pour point characteristicsare considered, gave the most acceptable l0W/30 multiviscosity oil. itis evident that polymers of the invention made from C to C alpha olefinscan be used to produce l0W/30 multiviscosity oil but best e l ser i s!itiit s pel r fr9 .925

TABLE V.-PREPARATION OF POLYMERS Polymer preparation Polymer proporties, viscosity Tem- Addiat Alpha pera- Moles Moles Moles tionReaction ratios olefin ture, moncatadilutime 100 F., 210 F., monomerCatalyst Diluent F. omer lyst ent hours A B C cs. cs,

Example:

2 Rescue-1.. 30 2.32 .13 16.1 4 17.8 6. 04 4.45 4,795 206 3.. 30 2. 32.13 16.1 2 17.8 6. 94 8. 9 3,023 148 4.. 30 11.0 06 16.1 12 183. 3 1. 4615. 3 1, 540 100 5.. 30 3. 19 08 19. 2 8 39. 9 6. 02 5. 0 2, 450 161 630 1. 50 .08 14. 8 8 18. 8 9. 87 2. 3 8, 200 463 7 .do..... 30 1.12 .084. 8 6 14.0 13.21 2. 3 3, 450 220 8 Dodecene-l 30 1. 08 15. 1 8 19. 4 9.74 2. 4 7, 844 531 9 ..do... 30 1.62 .07 16.1 4 23.2 9.94 5.8 1,000 7910 Tetratiec- 30 1. 36 08 13. 1 8 17. 0 9. 63 2. 1 2,034 161 ene- 11Hexedlec- .do do. 30 1.35 .08 15.1 8 16.0 11.19 2.1 1,869 157 ene- * HClbubbled through diluent-catalyst mix for /5 hour prior to monomeraddition; A=Moles of alpha olefin per mole of AlCla;

B=Moles of butane per mole of olefin; O=Moles of alpha olefin per moleof A101; per hour.

When l5 percent by volume of polymers prepared from C to C alpha olefinswas added to the hydroflnished light neutral distillate oil theresultant blend had viscosities in the range required for l0W/30multiviscosity oils. The result obtained when blending 15 volume percentof the polymers with arc ul fii lid. were v. tern.

While polymers of normal alpha olefins having from about six to 16carbon atoms per molecule have been described above with particularreference to their ability to improve the viscosity index ofhydrofinished and hydrotreated mineral lubricating oils, it is to beunderstood that the polymers can also be utilized in improving theviscosity index of other mineral lubricating oils. For example, thepolymers can be added to lubricating oils that have been derived fromparaffinic, naphthenic or mixed base crude petroleum oils, and that havebeen subjected to solvent or sulfuric acid treatment, aluminum chloridetreatment and other refining treatments. The improved characteristics ofother hydrotreated and nonhydrotreated base oils with other polymers ofthe invention TxBLi'iHiIREsPoNsE OF LIGHT NEUTRAL DIS'IILLA'IE T0VARIOUS o POLYMERS Composition Percent by volume of Light neutraldistillate Cm polymer. Medium Gm Polymer Light On polymer. Inspeciions;Viscosity; cs. at:

F Viscosity index, D567- Meets specifications. After 10 minutes soni es.at:

TABLE VIII.EFFECT OF POLYMER ON VISCOSITY F TABLE Xi l BASE OILS Cpltilyniietrz I t t 100 F. 4000 15 Polymer. y as a 01 o Viscosity: cs.at 100 F. 8600 7 5005 0 i V1 ml: "at 210 F. 542 5 iscosity index,D507122 Vl. .osity liirlex, l)567120 viscosity, CS

B... on 250.2% "77551715 Viscosity, (1s. Vls- 5 O m Spoon-l I Il'olynn-r, icoiilty Mlitill llficrllltwn percen F. F. F. D561 cationslww. 0| vu time 0 100 211] nt ex, spec i- H t t rlcsarl itlmi ii-remit.l", |i l U507 cations l0 gt ifgfi fff fli 1 2 i i l 70 mmhlxm V n 14.873. 22 88 Extrapolated values.

8.0 a 21. 91 5. 21 143 5W/20 h V 18.0 1, 828 67.89 11.50 143 W/30 e A .Mllyitlrotroated 0 24 43 4 91 140 o l 1. t y

1.4 783 27-71 5.41 144 u TABLE XII. EFFECT OF POL! MER ON ISCOSIT} ()F2.9 804 30.29 5.90 145 5w/20 BASE OIL 11.5 1, 590 59.15 10. 42 145l0W/30 Ca polymer: lScOSltyI cs. at100 F. 1,215

. o l lqxtriipoluted values. 123321211 351?15%.?11.

Viscosity, es. \is- Polymer, cosity Meets Base oll volume 0 100 210index. specifi- D O TABLE IX.EFFEOT or POLYMER 0N VISCOSITY 0F descrlpmPercent F. D 1 ations BASE OILS 0 1,695 43. 05 7.02 132 10W/20Hydrotreated 5.0 1, 780 48. 7.865 132 10W/29 C15 polymer: 25 o l 10.02,000 55.6 8.77 132 10W/20 Viscosity: cs. at 100 F. 8,200 15. 0 2,56065. 8 10.16 134 10W/30 Viscosity: cs. at 210 F. 463 Viscosity index,D567 122 1 Extrapolated values.

Viscosity, cs. Vits- M t V Polymer cosi y ee 5 Base volum O 100 210index, Specifk The lubricat ng oil compositions of this invention cancondescription percent F. F. F. D567 cations tain other addition agentsnormally added to lubricating OilS for a specific purpose such as anoiliness agent, an extreme 50 Texas ressure a cut, an antioxidant, acorrosion inhibitor, a foam (11 till i 0 228 l) 675 2 34 49 p g S a e434 22 1 117 1:1: suppressant, a dye, a sludge inhibitor, a pour pointdepressant 9.8 555 27.55 5.88 159 5W/29 35 and the like. Light neutral912 157 low/20 While our invention has been described with reference todistillate 0 825 21.8 4.12 07 various specific examples and embodimentsit will be un- Wdium new 3 63-85 28 137 10W] 30 I derstood that theinvention is not limited to such examples and trril distillate. 8 g, 35833.3 5.22 .u m embodiments and may be variously practiced within thescope 9. 15.0 s, 529 142. 2 17.14 125 20W 59 40 of the clalms heremaftermade- We claim: 6 i; igg'f 3; 1. A lubricating composition comprising amajor amount of 9.5 223.1 17. 26 a mineral lubricating oil and a minoramount, sufficient to im- Hm TN 0" n 21 5 3 m prove the viscosity indexof said oil, of a polymer of a normal 1.8 1:800 34.7 5. alpha olefinhaving about four to about 16 carbon atoms per 3 3-33 molecule, saidpolymer being obtained by the process which comprises polymerizing saidolefin in the liquid phase in the 4 "iiiff 2'3: Presence of aluminumchloride and a nonpolymerizing 9:1) 2: 170 54:0 13:47 130 10W/20hydrocarbon diluent, said olefin being introduced into the alu- 50 minumchloride'nonpolymerizing hydrocarbon reaction mass 100 4 tr ll. 0 20.93.80 54 mm m 0 4.9 1, 260 29. 9 5.30 121 1. at a rate of about 0.6 toabout moles of said olefin per mole 2-: 551% 2 3 22 5 5838138 ofaluminum chloride per hour and in an amount of about 2 to Hydrotmatedabout 200 moles of olefin per mole of aluminum chloride, at a 011 0 1,3438-30 low/20 temperature of about 40 to about F. for a time suffi- 5. 21, 010 56. 03 0. 07 136 iow zo 55 cient to produce a polymer having aviscosity of about 40 to l t 1 t d I about 3,000 centistokes at 210 F. 5a ...Y%. 4 2. The lubricating composition of claim 1 wherein said minoramount is about 2 to about 30 ercent b volume of the P Y composition. 603. The lubricating composition of claim 1 wherein said TABLE X C Iolefin utilized in obtaining said polymer IS hexenel.

0 p0 ymer: l viscosity: w at 5950 4. The lubricating composition ofclaim 1 wherein said Viscosity: es. at 210 F. 380.7 olefin utilized inobtaining said polymer is octenel. Viscosity lndex' D567115 5. Thelubricating composition of claim 1 wherein said Viscosity, cs. Vis- M 5olefin utilized in obtaining said polymer is decenel. Pol mer cosltyeets Base on vgmm 0 100 210 index specify 6. The lubricating compositionof claim 1 wherein said description percent F. F. F. D567 cation olefinutilized n obtaining said polymer 1S dodecenel 0 869 5 M0 138 n 7. Thelubricating composition of claim 1 wherein said 10. 0 .122 2:1 g g 33 186 6128 0 olefin utilized in obtaining said polymer is tetradecene-l.15.0 2, 7 Hvdmtmated 0 1' 195 4 M0 132 low/20 0. The lubricatingcomposition of claim 1 wherein said oil 10. 0 2,170 59. 54 i1. 33 10W/a0olefin utilized in obtaining said polymer is hexadecene-l.

8 Mfg gig? &3; i3? $331138 9. The lubricating composition of claim 1wherein said a. 25 1, 359 59. 25 9. 79 30 low/30 olefin utilized inobtaining said polymer is an alpha olefin mixig m values 75 ture wherethe average carbon number of said mixture lS about four to about 16.

mass at a rate of about 2 to about l2 moles of decene-l per mole ofaluminum chloride per hour and in an amount of about 10 to about l00moles of decene-l per mole of aluminum chloride, at a temperature ofabout 25 to about 35 F. for a time sufficient to produce a polymerhaving a viscosity of about 40 to about 3,000 centistokes at 210 F.

t i i l i

2. The lubricating composition of claim 1 wherein said minor amount isabout 2 to about 30 percent by volume of the composition.
 3. Thelubricating composition of claim 1 wherein said olefin utilized inobtaining said polymer is hexene-1.
 4. The lubricating composition ofclaim 1 wherein said olefin utilized in obtaining said polymer isoctene-1.
 5. The lubricating composition of claim 1 wherein said olefinutilized in obtaining said polymer is decene-1.
 6. The lubricatingcomposition of claim 1 wherein said olefin utilized in obtaining saidpolymer is dodecene-1.
 7. The lubricating composition of claim 1 whereinsaid olefin utilized in obtaining said polymer is tetradecene-1.
 8. Thelubricating composition of claim 1 wherein said olefin utilized inobtaining said polymer is hexadecene-1.
 9. The lubricating compositionof claim 1 wherein said olefin utilized in obtaining said polymer is analpha olefin mixture where the average carbon number of said mixture isabout four to about
 16. 10. A lubricating composition comprising a majoramount of mineral lubricating oil and a minor amount, sufficient toimprove the viscosity index of said oil, of a polymer of decene-1, saidpolymer being obtained by the process which comprises polymerizing saiddecene-1 in the liquid phase in the presence of aluminum chloride andbutane as a diluent, said decene-1 being introduced into the aluminumchloride-butane reaction mass at a rate of about 2 to about 12 moles ofdecene-1 per mole of aluminum chloride per hour and in an amount ofabout 10 to about 100 moles of decene-1 per mole of aluminum chloride,at a temperature of about 25* to about 35* F. for a time sufficient toproduce a polymer having a viscosity of about 40 to about 3,000centistokes at 210* F.